CN109071730A

CN109071730A - High molecular material and its manufacturing method and polymerizable monomer composition

Info

Publication number: CN109071730A
Application number: CN201780017993.5A
Authority: CN
Inventors: 原田明; 高岛义德; 岩曾恭; 岩曾一恭
Original assignee: Osaka University NUC
Current assignee: Osaka University NUC
Priority date: 2016-03-18
Filing date: 2017-02-28
Publication date: 2018-12-21
Anticipated expiration: 2037-02-28
Also published as: CN109071730B; US11535691B2; JP2020073660A; WO2017159346A1; JP7054244B2; US20220169768A1; JP6636610B2; JPWO2017159346A1

Abstract

The present invention, which provides, a kind of has high tenacity and with self-repairability and can be by high molecular material and its manufacturing method that easy process is manufactured.The high molecular material includes by cross-linked polymer made of the mutual interaction crosslinking of main group and guest moieties.Cross-linked polymer includes the constitutional repeating unit that following general formulas (1a) and general formula (2a) indicate.[chemical formula 1][chemical formula 2]

Description

High molecular material and its manufacturing method and polymerizable monomer composition

Technical field

The present invention relates to high molecular material and its manufacturing method and polymerizable monomer compositions.

Background technique

The research and development of the high molecular materials such as high-molecular gel are prevailing so far, apply flexibly its characteristic and are applied to industrial neck The various uses such as domain, medical field, field of food.As high-molecular gel, for example, it is known be crosslinked made of three-dimensional cross-linked it is high Water, so-called hydrogel are maintained in molecule.Especially in recent years, it had attempted to by being reviewed one's lessons by oneself to high-molecular gel imparting The functions such as renaturation or shape memory are to realize the further high performance of high-molecular gel.

Pass through the mutual covalent bond of chain macromolecule usually as the cross-linked polymer for the matrix for constituting high-molecular gel It is crosslinked and forms tridimensional network.Therefore, when applying stress to high-molecular gel, which is easy to concentrate on three-dimensional netted Shorter part, therefore it is easy to happen material breakage.Moreover, if the key of three-dimensional netted crosslink part is once cut off, due to It can not be bonded as before and (be bonded again), therefore also be difficult to carry out selfreparing.

It is proposed from such angle, such as patent document 1 using the macromolecule with main group and is had The high molecular so-called Host-guest of guest moieties interacts and is formed the technology of high-molecular gel.For such height For molecular gel, even if assuming that high-molecular gel is cut off, it can also be interacted by Host-guest and carry out key again It closes, therefore is self-repair function and the excellent material of shape memory function.

Existing technical literature

Patent document

Patent document 1: International Publication No. 2013/162019

Summary of the invention

The technical problem to be solved in the present invention

On the other hand, in recent years, also it is desirable to which high-molecular gel as described above is high tenacity.As long as high-molecular gel can With such high tenacity, then become the material of the strength of materials and excellent in te pins of durability, at the same with regard to usage more extensively this The very high material of utility value can also be become for point.From such angle, it is expected that developing one kind both has selfreparing Performance has the high-molecular gel of high tenacity again.

Have high tenacity the present invention has been made in view of the above-described circumstances, and an object thereof is to provide one kind and there is selfreparing Property and can be by high molecular material and its manufacturing method that easy process is manufactured.In addition, its purpose is also resided in and is mentioned For a kind of polymerizable monomer composition as the raw material for being suitable for obtaining above-mentioned high molecular material.

Solve the technological means of technical problem

Further investigation has been repeated in present inventor in order to achieve the above objectives, as a result, it has been found that, by so-called Host-guest interaction and formed high molecular material in, especially by by the main body of specific structure and object importing Macromolecular scaffold can reach above-mentioned purpose, so as to complete the present invention.

That is, the present invention such as theme comprising being recorded in following items.

1. a kind of high molecular materials of item, for comprising being crosslinked by the interaction of main group and guest moieties Cross-linked polymer high molecular material,

The cross-linked polymer includes the constitutional repeating unit that following general formulas (1a) and general formula (2a) indicate.

[chemical formula 1]

In formula (1a), Ra indicates hydrogen atom or methyl, R^HIndicate main group, R¹Indicate hydroxyl, sulfydryl, can have 1 with On substituent group alkoxy, can have 1 or more substituent group thio alkoxy, can have 1 or more substituent group Alkyl, the amino that can have 1 substituent group, the amide groups that can have 1 substituent group, by from selected from being made of aldehyde radical and carboxyl Group in univalent perssad in remove 1 hydrogen atom and the bivalent group that is formed.

[chemical formula 2]

In formula (2a), Ra indicates hydrogen atom or methyl, R^GIndicate guest moieties, R²Indicate hydroxyl, sulfydryl, can have 1 with On substituent group alkoxy, can have 1 or more substituent group thio alkoxy, can have 1 or more substituent group Alkyl, the amino that can have 1 substituent group, the amide groups that can have 1 substituent group, by from selected from being made of aldehyde radical and carboxyl Group in univalent perssad in remove 1 hydrogen atom and the bivalent group that is formed.

2. high molecular materials according to above-mentioned item 1 of item, wherein the main group is selected from by alpha-cyclodextrin, β- At least one of the group of cyclodextrin and gamma-cyclodextrin composition.

3. high molecular materials according to above-mentioned item 1 or 2 of item, wherein the main group is alpha-cyclodextrin, the visitor Body group is at least one of the group selected from octyl and dodecyl.

4. high molecular materials according to above-mentioned item 1 or 2 of item, wherein the main group is beta-cyclodextrin, the visitor Body group is at least one of the group selected from adamantyl and isobornyl.

5. high molecular materials according to above-mentioned item 1 or 2 of item, wherein the main group is gamma-cyclodextrin, described Guest moieties are at least one of the group selected from octyl and dodecyl.

6. a kind of manufacturing methods of high molecular material of item, to include the interaction for passing through main group and guest moieties And the manufacturing method of the high molecular material of cross-linked polymer made of being crosslinked,

The polymerization of its mixture for having the polymerizable monomer by the inclusion of following general formulas (1b) and general formula (2b) expression React the process for obtaining the cross-linked polymer.

[chemical formula 3]

In formula (1b), Ra indicates hydrogen atom or methyl, R¹And R^HRespectively with the R of above-mentioned general formula (1a)¹And R^HIt is identical.

[chemical formula 4]

In formula (2b), Ra indicates hydrogen atom or methyl, R²And R^GRespectively with the R of above-mentioned general formula (2a)²And R^GIt is identical.

The manufacturing method of 7. high molecular materials according to above-mentioned item 6 of item, wherein the mixture includes by described The interaction of the guest moieties of the main group and general formula (2b) of general formula (1b) and by the general formula (1b) and general formula The inclusion compound that the polymerizable monomer that (2b) is indicated is formed.

8. a kind of polymerizable monomer compositions of item, for for manufacturing polymerism list used in the raw material of high molecular material Body composition, it includes the polymerism lists that following general formulas (1b) polymerizable monomer indicated and following general formula (2b) indicate Body.

[chemical formula 5]

[chemical formula 6]

9. polymerizable monomer compositions according to above-mentioned item 8 of item, it includes indicate poly- by the following general formula (1b) The interaction for the guest moieties of polymerizable monomer that the main group of conjunction property monomer is indicated with the following general formula (2b) and by described The inclusion compound that the polymerizable monomer that the polymerizable monomer and the general formula (2b) that general formula (1b) indicates indicate is formed.

[chemical formula 7]

[chemical formula 8]

10. a kind of polymerizable monomers of item, to include the interaction for passing through main group and guest moieties for manufacturing And the polymerizable monomer of the high-molecular gel of cross-linked polymer made of being crosslinked, it is indicated by following general formulas (1b).

[chemical formula 9]

In formula (1b), Ra indicates hydrogen atom or methyl, R^HIndicate main group, R¹Indicate hydroxyl, sulfydryl, can have 1 with On substituent group alkoxy, can have 1 or more substituent group thio alkoxy, can have 1 or more substituent group Alkyl, the amino that can have 1 substituent group, the amide groups that can have 1 substituent group, by from selected from being made of aldehyde radical and carboxyl Group in univalent perssad in remove 1 hydrogen atom and the bivalent group that is formed.

A kind of preparation methods of the polymerizable monomer replaced through host molecule of item 11. comprising in the presence of acid catalyst Under, the polymerizable monomer that indicates the following general formula (5) and the host molecule process that carries out dehydrating condensation in a solvent.

[chemical formula 10]

In formula (5), Ra indicates hydrogen atom or methyl, R¹Indicate hydroxyl, sulfydryl, can have 1 or more substituent group alkane Oxygroup, can have 1 or more substituent group thio alkoxy, can have 1 or more substituent group alkyl, can have 1 The amino of substituent group, passes through the monad radical from selected from the group being made of aldehyde radical and carboxyl at the amide groups that can have 1 substituent group The bivalent group for removing 1 hydrogen atom in group and being formed.

Invention effect

High molecular material of the invention has high tenacity, is the material of mechanical strength, while being also equipped with self-repairability.

In addition, the manufacturing method of high molecular material of the invention is to be suitble to the method for the above-mentioned high molecular material of manufacture, it can With easy process and cheap price manufactures high molecular material.

Polymerizable monomer composition of the invention is the raw material suitable for manufacturing the high molecular material for having high tenacity, if using High tenacity and the high molecular material with self-repairability can be then easily manufactured in the raw material.

Detailed description of the invention

Fig. 1 is the ideograph for indicating the appearance of the Host-guest interaction in cross-linked polymer.

Fig. 2 is the stress-strain diagram (fracture strength curve) of the high-molecular gel of Examples 1 to 6.

Fig. 3 is the fracture strength curve of the high-molecular gel of comparative example 1~4.

Fig. 4 is the fracture strength curve of previous acrylamide gel (methylene-bisacrylamide crosslinking).

Fig. 5 is the fracture strength curve of the high-molecular gel of embodiment 7.

Fig. 6 is the chart for indicating the result of the fracture strength of high-molecular gel of embodiment 7.

Fig. 7 is the fracture strength curve of the high-molecular gel of comparative example 6.

Fig. 8 is the chart for indicating the result of the fracture strength of high-molecular gel of comparative example 6.

Fig. 9 is Examples 1 to 6, the α high-molecular gel of comparative example 1~4 and (the methylene-bisacrylamide crosslinking of AAm gel Acrylamide gel) stress characteristics result summary.

Figure 10 is that (methylene-bisacrylamide is handed over for Examples 1 to 6, the α high-molecular gel of comparative example 1~4 and AAm gel Bipropenyl acrylamide gel) emergent property result summary.

Figure 11 is the result of the repeat pull of α CDAAmMe-Dod gel (3,3) and α CDAAm-Dod gel (3,3).

Figure 12 is the chart for indicating the result of the fracture strength of high-molecular gel of embodiment 8.

Figure 13 is the chart for indicating the result of the fracture strength of high-molecular gel of comparative example 5.

Figure 14 is the chart for indicating the result of the fracture strength of xerogel of embodiment 10.

Figure 15 is the chart for indicating the result of the fracture strength of xerogel of embodiment 11.

Figure 16 is the chart for indicating the result of the fracture strength curve of xerogel of acrylamide gel (TEGAA crosslinking).

Figure 17 is the chart for indicating the result of the fracture strength of high-molecular gel of embodiment 12.

Figure 18 is the photo for indicating the appearance evaluated the physical property of the high-molecular gel of embodiment 7, and (a) indicates to pierce through The appearance of test, (b) indicate that the appearance at tension test initial stage, (c) indicate that the appearance after tension test, (d) expression review one's lessons by oneself retrial The appearance tested.

Figure 19 indicate α CDAAmMe-Bu gel (x, y), α CDAAmMe-Hex gel (x, y) fracture strength measurement knot Fruit.

Figure 20 indicates β CDAAmMe-Ib gel (x, y), β CDAAmMe-Ad gel (x, y), β CDAAmMe-HAdA gel The measurement result of the fracture strength of (x, y), β CDAAmMe-EtAdA gel (x, y).

Figure 21 indicates the return rate measurement result of the various xerogel of embodiment 10,11,17,18.

Figure 22 indicates the temperature of the return rate after T=2 days of xerogel ((x, y)=(2,2)) obtained in embodiment 10 Dependence.

Figure 23 is indicated after cutting off xerogel obtained in embodiment 10 ((x, y)=(2,2)), in the environment of 100 DEG C Make the relationship of the recovery time and return rate when its recovery.

Specific embodiment

Hereinafter, the embodiment of the present invention will be described in detail.In addition, in this specification, about " containing " and " packet Containing " expression, including " containing ", "comprising", the concept of " substantially including " and " only including ".

< high molecular material >

The high molecular material of present embodiment includes to be crosslinked by the interaction of main group and guest moieties Cross-linked polymer.Particularly, the cross-linked polymer includes the following general formula (1a) and the repetition knot that the following general formula (2a) indicates Structure unit.

[chemical formula 11]

[chemical formula 12]

The high molecular material constituted in the above described manner has high tenacity, therefore is the material of mechanical strength.

In addition, though the annotation only made provision against emergencies, the Ra of formula (1a) and the Ra of formula (2a) can be mutually the same, Huo Zheye It can be different from each other.

As the concrete example of above-mentioned high molecular material, high-molecular gel can be enumerated, further, it is also possible to enumerate as height The xerogel of the hirudo leech of molecular gel.In addition to this, as above-mentioned high molecular material, it can also enumerate in coating and include The adhesive composition for including in epithelium ingredient or adhesive, but not limited to this.Particularly preferred high molecular material is macromolecule Gel, at this point, more particularly to apply flexibly the above-mentioned characteristic of high molecular material.

Cross-linked polymer is the matrix components of high molecular material.Cross-linked polymer is formed by the crosslinked polymer of chain, With so-called tridimensional network.

Cross-linked polymer will pass through the weight of main group and formula (2a) expression in the constitutional repeating unit of formula (1a) expression The interaction of guest moieties in complex structure unit, the key formed by Host-guest interaction are as crosslinking points To form cross-linked structure.Host-guest interaction can for example pass through the hydrophobicity phase interaction of main group and guest moieties With, hydrogen bond, molecular separating force, electrostatic interaction, coordinate bond, pi-electron interaction etc. and generate, but not limited to this.

Main group (the R in constitutional repeating unit that formula (1a) indicates^H) it is from can be with aftermentioned guest moieties (R^G) into The functional group of the host molecule of row Host-guest interaction.The type of such host molecule is not particularly limited.

As host molecule, can exemplify selected from alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, cup [6] arene-sulfonic acids, cup [8] arene-sulfonic acids, 12- crown ether -4,18- crown ether -6, [6] paracyclophane, [2,2] paracyclophane, cucurbit [6] urea and cucurbit [8] At least one of group of urea.The host molecule that these illustrations are enumerated can also further have substituent group.

It is preferred that host molecule is at least one of the group selected from alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin.Pass through this A little host molecules and when forming main group, Host-guest interaction is not easy to eliminate, and is as a result easy into the height of non-excellent tenacity Molecular gel.

Herein, in the present specification, the host molecules such as alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin are referred to as sometimes and are led Body group.Exactly, a hydrogen atom or a hydroxyl are removed from the molecules such as alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin Group based on univalent perssad after base in this specification is for convenience called as described above sometimes.

In formula (1a), work as R¹When the bivalent group formed to remove 1 hydrogen atom from alkoxy, as the alcoxyl Base can exemplify the alkoxy that carbon atom number is 1~10, specifically, methoxyl group, ethyoxyl, propoxyl group, isopropyl can be enumerated Oxygroup, butoxy, isobutoxy, sec-butoxy, amoxy, hexyloxy etc., they can be appointing in straight-chain and branched One.

In formula (1a), work as R¹When the bivalent group formed to remove 1 hydrogen atom from thio alkoxy, as the sulphur For alkoxy, carbon atom number can be exemplified and be 1~10 thio alkoxy, specifically, can enumerate methyl mercapto, ethylmercapto group, Rosickyite base, isopropyisulfanyl, butylthio, isobutylthio, secondary butylthio, penta sulfenyl, own sulfenyl etc., they can be straight-chain and branch Any one of chain.

In formula (1a), work as R¹It, can as the alkyl when bivalent group formed to remove 1 hydrogen atom from alkyl The alkyl that carbon atom number is 1~30 is exemplified, specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl can be enumerated Base, sec-butyl, tert-butyl, amyl, isopentyl, neopentyl, hexyl etc., they can be any in straight-chain and branched Person.

In formula (1a), if R¹The bilvalent radical formed to remove 1 hydrogen atom from the amino that can have 1 substituent group Group, then the nitrogen-atoms of amino can be with the carbon atom bonding of main chain (C-C key).

In formula (1a), if R¹The bilvalent radical formed to remove 1 hydrogen atom from the amide groups that can have 1 substituent group Group, then the carbon atom of amide groups can be with the carbon atom bonding of main chain (C-C key).

In formula (1a), if R¹The bivalent group formed to remove 1 hydrogen atom from aldehyde radical, then the carbon atom of aldehyde radical can With the carbon atom bonding of main chain (C-C key).

In formula (1a), if R¹The bivalent group formed to remove 1 hydrogen atom from carboxyl, then the carbon atom of carboxyl can With the carbon atom bonding of main chain (C-C key).

In formula (1a), as R¹, preferably from hydroxyl, carboxyl, can have and remove 1 hydrogen original in the amide groups of 1 substituent group Son and bivalent group, i.e. preferably respectively-O- (ehter bond), any in-COO- (ester bond) and-CO-NH- (amido bond) formed Person removes 1 hydrogen atom and the bivalent group (- CO-NH-) that is formed particularly preferably from the amide groups that can have 1 substituent group.

Guest moieties (the R in constitutional repeating unit that formula (2a) indicates^G) be can be with above-mentioned main group (R^H) led The guest molecule of body-object interaction is replaced in side chain and the functional group that is formed.The type of such guest molecule is without spy It does not limit.

As guest molecule, the chain or cricoid hydrocarbon and its 01 derivatives that carbon atom number is 4~18 can be exemplified；Aryl Compound；Carboxylic acid derivates；Ammonia derivative；Azobenzene derivatives with cyclic alkyl or phenyl；Cinnamic acid derivative；Fragrance Compounds of group and its 01 derivatives；Amine derivative；Ferrocene derivatives；Azobenzene；Naphthalene derivatives；Anthracene derivant；Pyrene derivatives: Derivative；The cluster that fullerene etc. is made of carbon atom；At least one of group selected from red sulfonyl compound.These illustrate column The guest molecule of act can also further have substituent group.

As above-mentioned carbon atom number be 4~18 hydrocarbon, can enumerate butane, hexane, hexamethylene, heptane, octane, nonane, The alkyl compounds such as decane, hendecane, dodecane, the tetradecane, pentadecane, hexadecane, heptadecane, octadecane, adamantane, arbitrarily Compound can be any one of straight-chain and branched.Furthermore it is possible to which having hydroxyl, carbon atom number is 4 or less (preferably Be 2 or less), carboxyl, the substituent groups such as amino.The hydrocarbon that above-mentioned carbon atom number is 6~18 can for example have 1~3 halogen atom (example Such as, fluorine, chlorine, bromine etc.), carboxyl, ester group, amide groups, can the substituent groups such as protected hydroxyl.In addition, above-mentioned carbon atom number be 6~ 18 hydrocarbon can have unsaturated bond.In addition, the hydrocarbon that above-mentioned carbon atom number is 6~18 can be to make as organometallic complex The alkyl that is bonded as substituent group of ferrocene.

It is preferred that guest molecule is the alkyl compound that carbon atom number is 4~18.Wherein, preferably carbon atom number is 6~12 Alkyl compound.At this point, Host-guest interaction is not easy to eliminate, it is as a result easily made into the high-molecular gel of excellent tenacity.This Outside, the alkyl compound that preferably carbon atom number is 4~18 is straight-chain, at this point, Host-guest interaction is not easy to eliminate, is tied Fruit easily becomes the especially excellent high-molecular gel of toughness.

In formula (2a), R²Definition and above-mentioned formula (1a) in R¹Identical, the mode being bonded with main chain (C-C key) is also identical.

In formula (2a), as R², 1 hydrogen atom is removed preferably from the amide groups that can have 1 substituent group and is formed Bivalent group, i.e.-CO-NH-, or remove preferably from carboxyl 1 hydrogen atom and the bivalent group, i.e.-COO- that is formed.

Cross-linked polymer can further include following logical in addition to formula (1a) and the constitutional repeating unit of (2a) expression The constitutional repeating unit that formula (3a) indicates.

[chemical formula 13]

In formula (3a), Ra indicates hydrogen atom or methyl, R³It indicates halogen atom, hydroxyl, sulfydryl, can have 1 substituent group Amino or its salt, can have 1 substituent group carboxyl or its salt or can have 1 or more substituent group amide groups or Its salt.

In addition, though the only annotation made provision against emergencies, for the Ra of formula (1a), the Ra of formula (2a) and formula (3a) Ra and Speech, more than the two in them can be identical or they can be different.

In formula (3a), if R³For the carboxyl with 1 substituent group, then can enumerate the hydrogen atom of carboxyl by alkyl (for example, Methyl, ethyl), hydroxyalkyl (for example, methylol, ethoxy), methoxy poly (ethylene glycol) (unit number of ethylene glycol be 1~20, it is excellent Be selected as 1~10, particularly preferably 2~5), (unit number of ethylene glycol is 1~20, preferably 1~10 to ethyoxyl polyethylene glycol, special You Xuanwei 2~5) etc. substituted carboxyls (that is, ester).

In formula (3a), if R³For the amide groups of the substituent group with 1 or more, as secondary amide or teritary amide, then can arrange Enumerate primary amide 1 hydrogen atom or 2 hydrogen atoms independently of one another by alkyl (for example, methyl, ethyl), hydroxyalkyl (for example, Methylol, ethoxy) replace amide groups.

In formula (3a), preferably R³For amino；Amide groups；The amide groups that hydrogen atom is replaced by alkyl, hydroxyl or alkoxy；Carboxylic Base；The carboxyl that hydrogen atom is replaced by alkyl, hydroxyalkyl (such as ethoxy) or alkoxy.At this point, constituting the friendship of high-molecular gel The structure of linked polymer becomes stable, and the physical property of high-molecular gel is easy to improve.

Cross-linked polymer for example can be by making the repetitive structure comprising above-mentioned formula (1a), formula (2a) and formula (3a) expression Unit and the polymer formed is cross-linked to each other and is formed.In addition, as long as crosslinking is poly- for the degree for not hindering effect of the invention Closing object also may include the polymer without main group and guest moieties.

In cross-linked polymer, each constitutional repeating unit can be arranged regularly, or can also be with random alignment.That is, Cross-linked polymer can be any one of block polymer, alternating polymer and atactic polymer, in addition it is also possible to for grafting Polymer.

In addition, as long as in a range that does not hinder the effect of the present invention, cross-linked polymer also may include other repetitions Structural unit for example also may include well known constitutional repeating unit.

Constitute the respective content ratio of constitutional repeating unit that the formula (1a), formula (2a) and formula (3a) of cross-linked polymer indicate It is not particularly limited.For example, all constitutional repeating units relative to cross-linked polymer, the repetition that can indicate formula (1a) Structural unit is set as 0.5~10 mole of %, formula (2a) constitutional repeating unit indicated is set as 0.5~10 mole of %.At this point, by In the interaction for being easy to produce main group and guest moieties, stable cross-linked structure easy to form, therefore tool easy to form There is the high-molecular gel of high tenacity and self-repairability.Relative to all constitutional repeating units of cross-linked polymer, more preferable formula The constitutional repeating unit that the constitutional repeating unit that (1a) is indicated is 0.5~6 mole of %, formula (2a) indicates is 0.5~6 mole of %, At this point, toughness and the high-molecular gel that self-repairability is further enhanced and the transparency is high can be obtained, purposes applicatory becomes It obtains more extensive.In cross-linked polymer, the constitutional repeating unit that particularly preferred formula (1a) indicates is 2~4 moles of %, formula (2a) indicates Constitutional repeating unit be 2~4 moles of %, be further enhanced and the high macromolecule of the transparency at this point, becoming self-repairability Gel, and be retractility also excellent high-molecular gel.

Further, as main group (R^H) when being functional group from alpha-cyclodextrin, relative to all of cross-linked polymer Constitutional repeating unit, preferred formula (1a) indicate constitutional repeating unit be 1~3 mole of %.At this point, becoming self-repairability into one Step is improved and the high high-molecular gel of the transparency, and is retractility also excellent high-molecular gel.In addition, working as main body base Group (R^H) when being functional group from beta-cyclodextrin, relative to all constitutional repeating units of cross-linked polymer, preferred formula The constitutional repeating unit that (1a) is indicated is 1~5 mole of %.At this point, becoming, self-repairability is further enhanced and the transparency is high High-molecular gel, and be retractility also excellent high-molecular gel.In addition, working as main group (R^H) it is from γ-ring paste When the functional group of essence, relative to all constitutional repeating units of cross-linked polymer, the repetitive structure list of preferred formula (1a) expression Member is 1~3 mole of %.At this point, becoming the high-molecular gel that self-repairability is further enhanced and the transparency is high, and to stretch Contracting also excellent high-molecular gel.

In addition, the constitutional repeating unit that formula (3a) indicates can be 80~99 moles of % in cross-linked polymer.At this point, by In the interaction for being easy to produce main group and guest moieties, therefore stable cross-linked polymer easy to form, and be easy to Obtain having high tenacity, self-repairability also excellent high-molecular gel.

Since cross-linked polymer is in main group of the side chain with the constitutional repeating unit indicated based on formula (1a) and in side Chain has the guest moieties based on formula (2a) constitutional repeating unit indicated, therefore Host-guest interaction can become crosslinking Point.Thus cross-linked polymer can be formed.

As an example, the structure of cross-linked polymer is shown in the following general formula (4).Herein, formula (1a) expression is shown Constitutional repeating unit in main group R^HBy being constituted from group made of one hydroxyl of removal in alpha-cyclodextrin, formula (2a) table Guest moieties R in the constitutional repeating unit shown^GThe R in constitutional repeating unit indicated for dodecyl, formula (3a)³For amide Base, the cross-linked polymer formed by the polymer of the random assortment of each constitutional repeating unit.In formula (4) ,-r- indicates each repetitive structure The random assortment of unit.

[chemical formula 14]

When for cross-linked polymer shown in formula (4), (one is removed from alpha-cyclodextrin in the alpha-cyclodextrin as main body Group made of hydroxyl) in inclusion have dodecyl as object, to form Host-guest interaction, can be made Cross-linked structure is formed for crosslinking points.Main group and guest moieties may be other combinations, can be identically formed with formula (4) Host-guest interaction.

As described above, in the cross-linked polymer of present embodiment, it is main possessed by the constitutional repeating unit that formula (1a) indicates Body group R^HWith via-O-CH₂(hereinafter, sometimes referred to as " linking group ") and and R¹The feature of bonding.Specifically, main body Group R^HWith the oxygen atoms bond of above-mentioned linking group, R¹One end and above-mentioned linking group carbon atom bonding.Due to main body base Group R^HBe bonded to side chain via the linking group, thus with no connection site the case where compared with, main group R^HFreedom degree It is high.Due to main group R as described above^HFreedom degree it is high, therefore become and be easy to generate main group R^HWith guest moieties R^G's The state of Host-guest interaction, as a result, cross-linked polymer easy to form, the variable morphology of high-molecular gel is obtained more Stablize.

Further, since high-molecular gel contains the cross-linked polymer formed as described above, high-molecular gel is aobvious Show high tenacity.High-molecular gel so shows that one of the reasons why high tenacity is, by above-mentioned main group R^HVia connection Group is bonded and bring high-freedom degree.That is, due to main group R^HFreedom degree it is high, therefore be not easy to cause main body-visitor The dissociation of body interaction, the toughness of high-molecular gel is got higher as a result, can become the high-molecular gel with excellent intensity. It is described in detail using Fig. 1.

Fig. 1 is the ideograph for indicating the appearance of the Host-guest interaction in cross-linked polymer, with the crosslinking of formula (4) It is illustrated for polymer.As shown in the drawing, the main group being bonded via linking group with polymer lateral chain (is pasted from α-ring Group made of hydroxyl is removed in essence) because linking group there are due to the main chain far from polymer and because of linking group In the presence of so that rotary freedom is also high.As a result, even if the crosslinking points in cross-linked polymer apply stress, guest moieties (12 Alkyl) it is also not easy to be detached from from main group, it thus can play high tenacity.

Therefore, the main body base eliminated is not easy if applying stress, Host-guest interaction to high-molecular gel The combination of group and guest moieties, it can be said that the toughness of high-molecular gel further increases, mechanical strength is especially excellent.From the angle Degree sets out, as the combination of main group and guest moieties, when the host molecule for constituting main group is alpha-cyclodextrin, preferably Guest moieties are at least one of the group selected from normal-butyl, n-hexyl, n-octyl and dodecyl, when composition main group Host molecule be beta-cyclodextrin when, preferably guest moieties be selected from adamantyl, hydroxyl replace adamantyl, ethyl replace gold Rigid at least one of alkyl and the group of isobornyl, when the host molecule for constituting main group is gamma-cyclodextrin, preferably Guest moieties are at least one of the group selected from n-octyl, dodecyl and cyclo-dodecyl etc..

As the solvent for including in high-molecular gel, aqueous solvent can be exemplified.Specifically, as aqueous solvent, it can Enumerate water outlet, water-soluble alcohol or their mixed solvent.

As long as high molecular material can also contain other additives, such as light for the degree for not hindering effect of the invention Stabilizer, dispersion stabilizer, electrolyte, binder etc..

The shape of high molecular material is not particularly limited, and can be formed in a manner of being adapted for use with purposes.For example, high score Sub- material can use well known means and be formed as sheet, membranaceous, blocky, plate, graininess etc..

The high molecular material of present embodiment includes the cross-linked polymer formed by Host-guest interaction, because This can also play the function of self-repairability.Although high molecular material shows high tenacity as described above, high molecular material can be because More than a certain amount of stress and be broken.Caused by the fracture is the elimination of the key by main group and guest moieties.However, for example When artificially fracture being made to be in contact with each other, being bonded for main group and guest moieties can be caused again.It can produce fracture as a result, Mutual to be bonded again, the high molecular material of fracture can carry out selfreparing.Further, since the high molecular material of present embodiment has Self-healing properties are also not easy residual and extend the trace generated so even extending high molecular material repeatedly.Due to high molecular material It has characteristics that, therefore the material particularly suitable as being used to form high-molecular gel.

Further, for the interaction of aforementioned body-object, due to be easy interaction is temporarily eliminated into Row includes again, therefore the high-molecular gel after being adhered by is easy the gel strength of initial stages of restoration.In addition, the bonding time is longer, by force Degree return rate can also become higher.

High molecular material can be made of the solvent seasoning for making to include in above-mentioned high-molecular gel, so-called xerogel State.Even if being such xerogel, also there is excellent toughness in the same manner as high-molecular gel.

The manufacturing method > of < high molecular material

By taking high-molecular gel as an example, to as described above comprising being handed over by the interaction of main group and guest moieties The manufacturing method of the high molecular material of cross-linked polymer made of connection is illustrated.

The manufacturing method of present embodiment has the polymerism by the inclusion of following general formulas (1b) and general formula (2b) expression The polymerization reaction of the mixture of monomer and the process for obtaining cross-linked polymer.In addition, hereinafter, general formula (1b) is indicated sometimes The polymerizable monomer that polymerizable monomer and general formula (2b) indicate writes a Chinese character in simplified form work " monomer (1b) " and " monomer (2b) " respectively.

[chemical formula 15]

[chemical formula 16]

In addition, though the annotation only made provision against emergencies, the Ra of formula (1b) and the Ra of formula (2b) can be mutually the same, Huo Zheye It can be different from each other.

Cross-linked polymer can be generated by above-mentioned polymerization reaction, and obtain the high score using the cross-linked polymer as matrix components Sub- gel.

Monomer (1b) is the polymerizable monomer that can form the constitutional repeating unit of above-mentioned formula (1a) expression.

In formula (1b), if R¹The bilvalent radical formed to remove 1 hydrogen atom from the amino that can have 1 substituent group Group, then the nitrogen-atoms of amino can be with the carbon atom bonding of C=C double bond.

In formula (1b), if R¹The bilvalent radical formed to remove 1 hydrogen atom from the amide groups that can have 1 substituent group Group, then the carbon atom of amide groups can be with the carbon atom bonding of C=C double bond.

In formula (1b), if R¹The bivalent group formed to remove 1 hydrogen atom from aldehyde radical, then the carbon atom of aldehyde radical can With the carbon atom bonding of C=C double bond.

In formula (1b), R¹When the bivalent group formed to remove 1 hydrogen atom from carboxyl, the carbon atom of carboxyl can be with The carbon atom bonding of C=C double bond.

Monomer (1b) is for example preferably (methyl) acrylate derivative (i.e. R¹Spread out for-COO-), (methyl) acrylamide Biology (i.e. R¹For-CONH-).At this point, polymerization reaction is easy to carry out, in addition, the toughness of obtained high-molecular gel can also become It is higher.In addition, in the present specification, (methyl) acrylic acid indicates any one of acrylic acid and methacrylic acid.

As being used to form main group (R^H) host molecule, be preferably selected from alpha-cyclodextrin, beta-cyclodextrin and γ-ring paste At least one of the group of essence.When forming main group by these host molecules, Host-guest interaction is not easy to eliminate, and ties Fruit is easily made into the high-molecular gel of excellent tenacity.Main group (R^H) it is from alpha-cyclodextrin, beta-cyclodextrin or gamma-cyclodextrin Remove univalent perssad made of a hydrogen atom or a hydroxyl.

Monomer (1b) for example can by with host molecule replace the following general formula (5) indicate polymerizable monomer hydroxyl or It is prepared by the hydrogen of the hydrogen atom of the hydroxyl.

[chemical formula 17]

In formula (5), Ra indicates hydrogen atom or methyl, R¹With the R of above-mentioned general formula (1a)¹It is identical.

For example, the polymerizable monomer replaced through host molecule: root can be obtained by the preparation method for having following processes The polymerizable monomer and host molecule in the presence of acid catalyst, in a solvent indicating general formula (5) according to needs are dehydrated The process of condensation.The polymerizable monomer replaced through host molecule is, for example, monomer (1b).

Host molecule is at least one of group selected from alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin (hereinafter, sometimes Only it is referred to as " cyclodextrin ") when, by the dehydrating condensation for the polymerizable monomer that cyclodextrin and formula (5) indicate, list can be prepared Body (1b).

Above-mentioned dehydrating condensation can for example carry out in the presence of acid catalyst.Acid catalyst is not particularly limited, can be wide It is general to use well known catalyst, such as p-methyl benzenesulfonic acid, aluminium chloride, hydrochloric acid can be enumerated etc..The usage amount of acid catalyst is opposite It for example can be 20 moles of % hereinafter, preferably 10 moles of % are hereinafter, can be 0.001 to rub relative to cyclodextrin in cyclodextrin You are % or more, preferably 0.01 mole of % or more, more preferably 0.1 mole of % or more.

Solvent in the reaction is also not particularly limited, for example, can enumerate water outlet, dimethylformamide, dimethyl sulfoxide, N-Methyl pyrrolidone etc..Especially from being easy to adjust the concentration of above-mentioned acid and being easy to control the angle of reaction, solvent is excellent It is selected as dimethylformamide, dimethyl sulfoxide, N-Methyl pyrrolidone, particularly preferably dimethylformamide.Dehydrating condensation Reaction temperature and reaction time also do not limit, and can be carried out with suitable condition.From the angle for carrying out reaction more quickly It sets out, preferable reaction temperature is 25~90 DEG C, and the reaction time is 1~3 hour.The further preferred reaction time is 5 minutes~1 small When.After above-mentioned reaction, it can be purified using well known purification means.

The method for preparing monomer (1b) is not limited to above-mentioned preparation method, additionally it is possible to be prepared using well known method. However, if can be prepared by the reaction in a stage monomer (1b), therefore as a result, energy using above-mentioned dehydrating condensation The whole preparation section for shortening high-molecular gel, can simplify the preparation section of high-molecular gel, so it is preferred that.

Monomer (2b) is the polymerizable monomer that can form the constitutional repeating unit of above-mentioned formula (2a) expression.

In formula (2b), R²Definition and above-mentioned formula (2a) in R¹It is identical, it is also identical as the bonding pattern of C=C double bond.

Monomer (2b) is for example preferably (methyl) acrylate or derivatives thereof (i.e. R¹For-COO-), (methyl) acryloyl Amine or derivatives thereof (i.e. R¹For-CONH-).At this point, polymerization reaction is easy to carry out, and the toughness of obtained high-molecular gel can also Become higher.

As the concrete example of monomer (2b), can enumerate (methyl) n-butyl acrylate, (methyl) the just own ester of acrylic acid, (methyl) n-octyl, (methyl) acrylic acid n-dodecane base ester, 1- acrylamide adamantane, N- dodecyl (methyl) Acrylamide, (methyl) tert-butyl acrylate, (methyl) acrylic acid n-dodecane base ester, 1- acrylamide adamantane, N- (1- gold Rigid alkyl) (methyl) acrylamide, N- benzyl (methyl) acrylamide, N-1- naphthyl methyl (methyl) acrylamide, ethyoxyl Change o-phenyl phenol acrylate, phenoxy group polyethylene glycol acrylate, acrylic acid iso stearyl ester, nonyl phenol EO addition product third Olefin(e) acid ester, isobornyl acrylate etc..

Monomer (2b) can be prepared using well known method.

The mixture of the polymerizable monomer indicated comprising formula (1b) and formula (2b) can also further include except formula (1b) and Other polymerizable monomers other than the polymerizable monomer that formula (2b) indicates.It as other polymerizable monomers, such as may include following General formula (3b) indicate polymerizable monomer.

[chemical formula 18]

In addition, hereinafter, general formula (3b) polymerizable monomer indicated is write a Chinese character in simplified form work " monomer (3b) " sometimes.

In formula (3b), Ra indicates hydrogen atom or methyl, R³With the R of above-mentioned general formula (3a)³It is identical.

In addition, though the only annotation made provision against emergencies, for the Ra of formula (1b), the Ra of formula (2b) and formula (3b) Ra and Speech, it is more than the two in them can it is identical or they and it is different.

Monomer (3b) is the monomer that can form the constitutional repeating unit of above-mentioned general formula (3a) expression.

As the concrete example of monomer (3b), (methyl) acrylic acid, (methyl) acrylamide, (methyl) acrylic acid can be enumerated Methyl esters, (methyl) ethyl acrylate, N, N- dimethacrylamide, N- isopropyl (methyl) acrylamide, N- methylol (first Base) acrylamide, N- methylol (methyl) acrylate, 2- ethoxy (methyl) acrylamide, (methyl) acrylic acid 2- hydroxyl Ethyl ester, ethyoxyl-diethylene glycol acrylate, methoxy-triethylene glycol acrylate, methoxypolyethylene glycol acrylate Deng.

As long as not hindering effect of the invention, polymerizable monomer can also contain demonomerization (1b), monomer (2b) and monomer Monomer other than the polymerizable monomer that (3b) is indicated.

The mix proportions of monomer (1b), monomer (2b) and monomer (3b) are not particularly limited.For example, relative to monomer The total amount of (1b), monomer (2b) and monomer (3b), monomer (1b) can be 0.5~10 mole of %, monomer (2b) can be 0.5~ 10 moles of %.At this point, due to the interaction for being easy to produce main group and guest moieties, stable crosslinking easy to form Polymer, and it is readily available with high tenacity, self-repairability also excellent high-molecular gel.Relative to monomer (1b), monomer The total amount of (2b) and monomer (3b), more preferable monomer (1b) is 1~5 mole of %, monomer (2b) is 1~5 mole of %.At this point, from The high-molecular gel that prosthetic is further enhanced and the readily available transparency is high, purposes applicatory become more extensively. Further, the total amount relative to monomer (1b), monomer (2b) and monomer (3b), particularly preferred monomer (1b) be 2~4 moles of %, Monomer (2b) is 2~4 moles of %.At this point, become the high-molecular gel that self-repairability is further enhanced and the transparency is high, and And readily available retractility also excellent high-molecular gel.

Further, as main group (R^H) when being functional group from alpha-cyclodextrin, relative to monomer (1b), monomer (2b) And the total amount of monomer (3b), preferred monomers (1b) are 1~3 mole of %.It is further enhanced and thoroughly at this point, becoming self-repairability The high high-molecular gel of bright property, and be retractility also excellent high-molecular gel.In addition, working as main group (R^H) it is from β- When the functional group of cyclodextrin, relative to the total amount of monomer (1b), monomer (2b) and monomer (3b), preferred monomers (2b) are rubbed for 1~5 You are %.In addition, working as main group (R^H) when being functional group from gamma-cyclodextrin, relative to monomer (1b), monomer (2b) and single The total amount of body (3b), preferred monomers (2b) are 1~3 mole of %.At this point, become self-repairability be further enhanced and the transparency High high-molecular gel, and be retractility also excellent high-molecular gel.

In addition, the total amount relative to monomer (1b), monomer (2b) and monomer (3b), monomer (3b) can rub for 80~99 You are %.At this point, due to the interaction for being easy to produce main group and guest moieties, stable cross-linked polymeric easy to form Object, and it is readily available with high tenacity, self-repairability also excellent high-molecular gel.

As the combination of monomer (1b) and monomer (2b), it is easy to carry out from polymerization reaction, and obtained high-molecular gel The angle that toughness is further enhanced, mechanical strength is especially excellent is set out, when the host molecule for constituting main group is α-ring When dextrin, preferably guest moieties are at least one of the group selected from normal-butyl, n-hexyl, n-octyl and dodecyl, when When the host molecule for constituting main group is beta-cyclodextrin, preferably guest moieties are in the group selected from adamantyl and isobornyl At least one, when constitute main group host molecule be gamma-cyclodextrin when, preferably guest moieties be n-octyl and positive 12 Alkyl, cyclo-dodecyl etc..

The polymerization reaction of the mixture of polymerizable monomer can be carried out using well known method.For example, in an aqueous solvent, it is poly- The polymerization reaction of said mixture is carried out in the presence of conjunction initiator.The mixture of polymerizable monomer polymerize and gives birth to as a result, At the cross-linked polymer as matrix components, high-molecular gel can be manufactured.

As above-mentioned aqueous solvent, it is able to use water.In addition to this, above-mentioned aqueous solvent can be lower alcohol, can also be with For the mixed solvent of lower alcohol and water.

The usage amount of above-mentioned aqueous solvent is not particularly limited, such as relative to the total amount of polymerizable monomer, aqueous solvent The lower limit of usage amount be more preferably 50 mass %, particularly preferably 60 mass %.At this point, being easily formed stable Macromolecule Glue is also less prone to the various physical property such as damage self-repairability.In addition, the total amount relative to polymerizable monomer, the usage amount of aqueous solvent The upper limit be more preferably 150 mass %, particularly preferably 99 mass %.

As above-mentioned polymerization initiator, such as can to enumerate ammonium persulfate (hereinafter, sometimes referred to as APS), azo two different Butyronitrile (hereinafter, sometimes referred to as AIBN), 2,2 '-azo two [2- (2- imidazoline -2- base) propane] dihydrochlorides are (hereinafter, have When also referred to as VA-044), 1,1 '-azos two (cyclohexyl nitrile), di-tert-butyl peroxide, tert-butyl hydroperoxide, peroxide Change benzoyl, Photoepolymerizationinitiater initiater (Irgacure (registered trademark) series etc.) etc..It is preferred that APS and VA-044.

In mixture used in above-mentioned polymerization reaction, relative to the total amount of polymerizable monomer, the concentration of polymerization initiator It can be 0.5~5 mole of %.

When carrying out above-mentioned polymerization reaction, it can according to need and add other additives.As other additives, can exemplify Polymerization accelerant, crosslinking agent etc..As above-mentioned polymerization accelerant, for example, N, N, N ', N '-tetramethylethylenediamine etc..For example, phase For the total amount of polymerizable monomer, the concentration of polymerization accelerant can be 0.5~5 mole of %.

The condition of polymerization reaction can be according to the half-life period temperature of the polymerism or usage amount of the monomer used, polymerization initiator Degree etc. is carried out with suitable condition.For example, can by by said mixture in 0~100 DEG C, be preferable over 20~25 DEG C and be stirred To carry out polymerization reaction.The time of polymerization reaction can be set to 1~24 hour, preferably can be set to 12~24 hours.In addition, will When Photoepolymerizationinitiater initiater is used as polymerization initiator, such as the UV light to 200~400nm of said mixture illumination wavelength can be passed through And carry out polymerization reaction.After carrying out polymerization reaction as described above, purified or dried as needed, cured etc., thus make Make high-molecular gel.

Herein, for above-mentioned polymerization reaction, can have before starting polymerization reaction in advance to monomer (1b) and monomer The process (heating process) that the mixture of (2b) is heated.By the heating process, cause main body possessed by monomer (1b) The interaction of group and guest moieties possessed by monomer (2b) can form the inclusion compound (packet of monomer (1b) and monomer (2b) Close complex).Process by having the mixture to monomer (1b) and monomer (2b) to be heated, monomer (1b) and monomer The mixture of (2b) is easy to become uniformly, and polymerization reaction rapidly carries out, and is also easy to form cross-linked structure, therefore can manufacture Crosslinking structural body with stable structure.Therefore, it can be said that the preferred embodiment of the manufacturing method of present embodiment is, polymerization is anti- The mixture of monomer used in answering (1b) and monomer (2b) pass through the main group of general formula (1b) and the object base of general formula (2b) The interaction of group forms the inclusion compound formed by monomer (1b) and monomer (2b).

In the process of heating monomer (1b) and the mixture of monomer (2b), heating temperature for example can be 20~100 DEG C. Preferred heating temperature is 50~80 DEG C.In addition, heating time is influenced by monomer (1b) and the combination of monomer (2b), such as can Think 1 minute~12 hours.The preferred reaction time is 15 minutes~1 hour.Heating means is also not particularly limited, such as The method using thermal agitation device, method using thermostat etc. can be enumerated.Can heating while implement ultrasonication, Or replace heating and implement ultrasonication, at this point, the inclusion compound of monomer (1b) Yu monomer (2b) is more readily formed, even if mixing The low complex that also can promote of the temperature of object is formed.

When heating to the mixture of monomer (1b) and monomer (2b), other polymerizable monomers such as monomer (3b) are used In the case of, monomer (3b) can be pre-mixed before heating to monomer (1b) and monomer (2b).Alternatively, can also be to list After the mixture of body (1b) and monomer (2b) are heated, mix monomer (3b).Further, to monomer (1b) and monomer (2b) Mixture when being heated, raw material used in the polymerization reactions such as aqueous solvent, polymerization initiator can be to monomer (1b) It is pre-mixed, can also be mixed before being heated with monomer (2b) after the heating.

About whether the inclusion compound for being formed with monomer (1b) Yu monomer (2b), for example, can observe by visual observation heating after The state of monomer (1b) and the solution of monomer (2b) is to be determined.Specifically, if not formed inclusion compound, monomer (1b) Mixture with monomer (2b) is suspended state or is the state for standing phase and separating, can be at if foring inclusion compound For the sticking state of the tool such as gluey or emulsus.In addition, being that group, guest moieties from beta-cyclodextrin are for main group Combination when isobornyl preferably carries out heating to the mixture comprising monomer (1b) and monomer (2b) to form inclusion compound. This is because there are complexs to be precipitated and be generated in the form of powder crystallization when mix monomer (1b) is with monomer (2b) at normal temperature The case where precipitating.

Using above-described manufacturing method, can obtain including cross-linked polymer and water by Host-guest interaction High-molecular gel, the i.e. so-called hydrogel for waiting aqueous solvents and being formed.

Obtained high-molecular gel includes formula (1a) and the constitutional repeating unit that formula (2a) indicates, therefore for high-ductility The material of property, mechanical strength.In addition, high-molecular gel includes to be gathered by the crosslinking that Host-guest interaction is formed Object is closed, therefore the function of self-repairability can be played.

Therefore, above-mentioned manufacturing method is suitable as the side that manufacture has high tenacity and has the high-molecular gel of self-repairability Method.In addition, above-mentioned manufacturing method can obtain well desired high-molecular gel with easy process efficiency.

In addition, when high molecular material is the material other than high-molecular gel, as long as using above-mentioned each monomer, manufacture Method is not particularly limited, such as can be using the polymerization carried out all the time.In addition, xerogel can be by making institute as above High-molecular gel obtained from stating further is dried under suitable drying condition and is obtained.

< polymerizable monomer composition >

The polymerism list that the polymerizable monomer (monomer (1b)) and general formula (2b) indicated comprising above-mentioned general formula (1b) indicates The polymerizable monomer composition of body (monomer (2b)) can use in the raw material for manufacturing high-molecular gel.If using in this way Polymerizable monomer composition, then high-molecular gel can be manufactured with easy process, and due to using the polymerizable monomer The high-molecular gel that composition obtains includes the constitutional repeating unit that formula (1a) and formula (2a) indicate, thus for high tenacity, The material of mechanical strength.

Polymerizable monomer composition preferably comprises the guest moieties of the main group and monomer (2b) by monomer (1b) The inclusion compound for interacting and being formed by monomer (1b) and monomer (2b).At this point, since monomer (1b) and monomer (2b) is easy It mixes evenly, polymerization reaction rapidly carries out, and be also easy to be formed cross-linked structure, therefore easily fabricated with stable structure Crosslinking structural body.

By carrying out heating and/or ultrasonication to polymerizable monomer composition, the master of monomer (1b) thus can be passed through The interaction of the guest moieties of body group and monomer (2b), forms the inclusion compound formed by monomer (1b) and monomer (2b).Add Hot method can be identical as the heating condition in above-mentioned heating process.

The polymerizable monomer composition of present embodiment is the raw material suitable for manufacturing the high-molecular gel for having high tenacity, if Using the raw material, then the high-molecular gel of high tenacity can be easily manufactured.

Embodiment

Hereinafter, being more specifically illustrated using embodiment to the present invention, but the present invention is not limited to these embodiments Mode.

(preparation example 1；The preparation of acrylamide methviium α cyclodextrin)

According to the scheme of following formulas (6-1), acrylamide methviium α cyclodextrin (α CDAAmMe) is prepared.

[chemical formula 19]

Into 300mL round-bottomed flask weighing alpha-cyclodextrin 20g (20mmol), N hydroxymethyl acrylamide 2g (20mmol) and P-methyl benzenesulfonic acid monohydrate 190mg (1mmol (10mol%)), and be added into the n,N-Dimethylformamide of 50mL, Prepare reaction solution.By the reaction solution oil bath heating to 90 DEG C, and heating stirring 1 hour.Then, reaction solution is let cool, and infused Enter in the acetone 500mL being vigorously stirred.After the precipitating that leaching generates, cleaned three times with the acetone of 100mL, by normal It is dried under reduced pressure one hour under warm (20 DEG C, same as below) and obtains reactant.The reactant is dissolved in distilled water 500mL, makes it By the color for being filled with expanded polystyrene resin (Mitsubishi Chemical Corporation Diaion HP-20) It composes column (apparent density 600g/L), it is made adsorb within 30 minutes.In addition, also being replaced sometimes using preparative high pressure liquid chromatography The chromatographic column and carry out separating-purifying.Then, solution composition is removed, new distilled water 500mL is made to pass through chromatographic column twice, it is right Polystyrene resin is cleaned, and unreacted alpha-cyclodextrin is thus removed.Then, make 30% methanol (or acetonitrile) aqueous solution 500mL twice, thus dissolves out the α CDAAmMe as target product by chromatographic column.By removing solvent under reduced pressure, obtain White powder 2.1g.Yield is about 10%.

(preparation example 2；The preparation of acrylamide methviium beta cyclodextrin)

According to the scheme of following formulas (6-2), acrylamide methviium beta cyclodextrin (β CDAAmMe) is prepared.

[chemical formula 20]

Weighing beta cyclodextrin 15g (15mmol), N hydroxymethyl acrylamide 2g into 200mL glass system round-bottomed flask (22.5mmol) and p-methyl benzenesulfonic acid monohydrate 500mg (2.6mmol, 1wt%), and be added into the N of 50mL, N- diformazan In base formamide, reaction solution is prepared.By reaction solution oil bath heating to 90 DEG C, and heating stirring 1 hour, thus reacted Liquid.Then, which is let cool, and be flowed into the acetone 45mL being vigorously stirred.After the precipitating that leaching generates, use The acetone cleaning of 10mL three times, obtains reactant and being dried under reduced pressure one hour at normal temperature.Reactant is dissolved in distillation Water 100mL makes it through filled with expanded polystyrene resin (Mitsubishi Chemical Corporation Diaion HP-20 chromatographic column (apparent density 600g/L)) makes it adsorb within 30 minutes.In addition, also using preparative high pressure liquid sometimes Phase chromatography replaces the chromatographic column and carries out separating-purifying.Then, solution composition is removed, new 10% methanol (or acetonitrile) water is made Solution 50mL three times, cleans polystyrene resin by chromatographic column, thus removes unreacted beta cyclodextrin.Then, make 25% methanol aqueous solution 500mL twice, thus dissolves out the β CDAAmMe as target product by chromatographic column.By by solvent Decompression removal, obtains white powder 156mg.Yield is about 13%.

(preparation example 3；The preparation of acrylamide methviium γ cyclodextrin)

Weighing γ cyclodextrin 5g (5mmol), N hydroxymethyl acrylamide 700mg into 200mL glass system round-bottomed flask (1.3mmol) and p-methyl benzenesulfonic acid monohydrate 95mg (0.5mmol), and be added into the n,N-Dimethylformamide of 25mL In, prepare reaction solution.By reaction solution oil bath heating to 90 DEG C, and heating stirring 1 hour, thus obtain reaction solution.Then, will The reaction solution is let cool, and is flowed into the acetone 45mL being vigorously stirred.It is clear with the acetone of 10mL after the precipitating that leaching generates It washes three times, obtains reactant and being dried under reduced pressure one hour at normal temperature.Reactant is dissolved in distilled water 100mL, makes it By the color for being filled with expanded polystyrene resin (Mitsubishi Chemical Corporation Diaion HP-20) It composes column (apparent density 600g/L), it is made adsorb within 30 minutes.In addition, also being replaced sometimes using preparative high pressure liquid chromatography The chromatographic column and carry out separating-purifying.Then, solution composition is removed, keeps new 10% methanol (or acetonitrile) aqueous solution 50mL logical It crosses chromatographic column three times, polystyrene resin is cleaned, thus remove unreacted beta cyclodextrin.Then, make 25% methanol water-soluble Liquid 500mL twice, thus makes the acrylamide methviium γ cyclodextrin (γ CDAAmMe) as target product molten by chromatographic column Out.By removing solvent under reduced pressure, white powder 809mg is obtained.Yield is about 15%.

(embodiment 1)

According to the scheme of following formulas (7-1-1), high-molecular gel is manufactured.In addition ,-r- indicates repetitive structure in scheme So-called random copolymer made of the random assortment of unit is also identical below.

[chemical formula 21]

In 5mL water, by obtained in preparation example 1 as the α CDAAmMe211mg of monomer (1b) with as monomer (2b) 48 μ L of dodecylacrylate (Dod-AA) mixed in a manner of the concentration for respectively becoming 2mol/kG, side irradiation is super It stirs at normal temperature 30 minutes on sound wave side.At this point, the character of reaction mixture is with Double-fluid separation state, emulsion, cream solid Sequence be changed.The acrylamide (AAm) as monomer (3b) is successively added into the mixture of lost flowability 682mg, ammonium persulfate (total mole number relative to all polymerizable monomers is 1mol%) and N as polymerization initiator, N, N ', N '-tetramethylethylenediamine (total mole number relative to all monomers is 1mol%) is placed 30 minutes at room temperature, To carry out polymerization reaction, and carry out gelation.The high-molecular gel α CDAAmMe-Dod comprising cross-linked polymer is obtained as a result, Gel (x, y).In addition, x, y respectively indicate constitutional repeating unit (1a) in cross-linked polymer, constitutional repeating unit (2a) Mol%.The x=2 of obtained high-molecular gel, y=2.

(embodiment 2~6)

In addition to become x shown in table 1, the mode of y is to the α CDAAmMe as monomer (1b) and as monomer (2b) Other than the usage amount of dodecylacrylate (Dod-AA) is adjusted, α is obtained using method same as Example 1 CDAAmMe-Dod gel (x, y).

[table 1]

(embodiment 7)

According to the scheme of following formulas (7-1-2), high-molecular gel is manufactured.

[chemical formula 22]

In 5mL water, by obtained in preparation example 1 as the α CDAAmMe211mg of monomer (1b) with as monomer (2b) 48 μ L of 2-ethyl hexyl acrylate (Oct-AA) mixed in a manner of the concentration for respectively becoming 2mol/kg, when irradiating ultrasonic wave It stirs 30 minutes at normal temperature.At this point, the character of reaction mixture is with Double-fluid separation state, the sequence of emulsion, cream solid It is changed.Acrylamide (AAm) 682mg, the work as monomer (3b) are successively added into the mixture of lost flowability For the ammonium persulfate (total mole number relative to all polymerizable monomers is 1mol%) and N, N, N of polymerization initiator ', N '- Tetramethylethylenediamine (total mole number relative to all monomers is 1mol%), places 30 minutes at room temperature to be gathered Reaction is closed, and carries out gelation.The high-molecular gel α CDAAmMe-Oct gel (x, y) comprising cross-linked polymer is obtained as a result,. In addition, x, y respectively indicate the mol% of constitutional repeating unit (1a) in cross-linked polymer, constitutional repeating unit (2a).It obtains The x=2 of high-molecular gel, y=2.Using same method, x=3, high-molecular gel, the x=1 of y=3, y=1 have also been made High-molecular gel, x=0.75, the high-molecular gel of y=0.75.

(comparative example 1)

In addition to the scheme according to following formulas (8-1), replaced in preparation example 1 using acrylamide α cyclodextrin (α CDAAm) Other than the obtained α CDAAmMe as monomer (1b), polymerization reaction is carried out using method same as Example 1.Acrylamide α cyclodextrin (α CDAAm) has from the nitrogen-atoms key for removing univalent perssad and acrylamide made of a hydroxyl in alpha-cyclodextrin The structure of conjunction.

[chemical formula 23]

High-molecular gel α CDAAm-Dod gel (x, y) is obtained as a result,.In addition, x, y respectively indicate the weight from α CDAAm The mol% of complex structure unit, constitutional repeating unit (2a).The x=3 of obtained high-molecular gel, y=3.

(comparative example 2~4)

In addition to become x shown in table 1, the mode of y is to α CDAAm and as the dodecylacrylate of monomer (2b) (Dod-AA) other than usage amount is adjusted, α CDAAm-Dod gel (x, y) is obtained using method identical with comparative example 1.

(embodiment 8)

According to the scheme of following formulas (7-2-1), high-molecular gel is manufactured.

[chemical formula 24]

In water, by the acrylamide methviium beta cyclodextrin (β CDAAmMe) obtained in preparation example 2 as monomer (1b) 24.4mg (20 μm of ol) and adamantane acrylamide (Ad-AAm) 4.8mg (20 μm of ol) as monomer (2b) is to respectively become The mode of the concentration of 2mol/kG is mixed, and is stirred 30 minutes at 80 DEG C when irradiating ultrasonic wave.Or with stirring at 80 DEG C Piece is mixed to be stirred.At this point, reaction mixture becomes transparent solution.Third as monomer (3b) is successively added into mixture Acrylamide (AAm) 198mg, as polymerization initiator ammonium persulfate (relative to always rubbing for all polymerizable monomersYouNumber is 1mol%) and N, N, N ', N '-tetramethylethylenediamine (relative to all monomers total mole number be 1mol%), at room temperature 30 minutes are placed to carry out polymerization reaction, and carries out gelation.The high-molecular gel β comprising cross-linked polymer is obtained as a result, CDAAmMe-Ad gel (x, y).In addition, x, y respectively indicate constitutional repeating unit (1a), repetitive structure list in cross-linked polymer The mol% of first (2a).The x=1 of obtained high-molecular gel, y=1.In addition, x=0.5 has also been made using same method, High-molecular gel, the x=3 of high-molecular gel, the x=2 of high-molecular gel, the x=0.75 of y=0.5, y=0.75, y=2, y= 3 high-molecular gel, x=4, high-molecular gel, the x=5 of y=4, high-molecular gel, the x=6 of y=5, the Macromolecule of y=6 Glue.

(embodiment 9)

According to the scheme of following formulas (7-2-2), high-molecular gel is manufactured.

[chemical formula 25]

In water, by the β CDAAmMe 24.4mg (20 μm of ol) obtained in preparation example 1 as monomer (1b) and as list The 4.3 μ L of isobornyl acrylate (Ib-AA) (20 μm of ol) of body (2b) is mixed in a manner of the concentration for respectively becoming 2mol/kG It closes, is stirred 30 minutes at 80 DEG C when irradiating ultrasonic wave.Or it is stirred at 80 DEG C with stirring sheet.At this point, reaction is mixed It closes object and becomes transparent solution.Acrylamide (AAm) 198mg as monomer (3b) is successively added into mixture, as poly- Close the ammonium persulfate (total mole number relative to all polymerizable monomers is 1mol%) and N, N, N of initiator ', N '-tetramethyl Base ethylenediamine is (relative to always rubbing for all monomersYouNumber is 1mol%), place 30 minutes at room temperature to polymerize instead It answers, and carries out gelation.The high-molecular gel β CDAAmMe-Ib gel (x, y) comprising cross-linked polymer is obtained as a result,.In addition, X, y respectively indicate the mol% of constitutional repeating unit (1a) in cross-linked polymer, constitutional repeating unit (2a).Obtained high score The x=1 of sub- gel, y=1.In addition, also having made x=0.5, high-molecular gel, the x=of y=0.5 using same method 0.75, y=0.75 high-molecular gel, x=2, high-molecular gel, the x=3 of y=2, the high-molecular gel of y=3.

(embodiment 10)

According to the scheme of following formulas (7-2-3), high-molecular gel is manufactured.

[chemical formula 26]

In water, by the acrylamide methviium beta cyclodextrin (β CDAAmMe) obtained in preparation example 2 as monomer (1b) 24.4mg (20 μm of ol) and adamantane acrylamide (Ad-AAm) 4.8mg (20 μm of ol) as monomer (2b) is to respectively become The mode of the concentration of 2mol/kG is mixed, and is stirred 30 minutes at 80 DEG C when irradiating ultrasonic wave.Or with stirring at 80 DEG C Piece is mixed to be stirred.At this point, reaction mixture becomes transparent solution.The first as monomer (3b) is successively added into mixture 400 μ L (1.98mmol) of oxygroup-triethyleneglycol acrylate (TEGAA), as polymerization initiator ammonium persulfate (relative to institute Some polymerizable monomers always rubYouNumber is 1mol%) and N, N, N ', N '-tetramethylethylenediamine is (relative to all monomers Always rubYouNumber is 1mol%), place 30 minutes at room temperature to carry out polymerization reaction, and carry out gelation.It is wrapped as a result, High-molecular gel β CDAAmMe-Ad gel (x, y) containing cross-linked polymer.In addition, x, y respectively indicate the weight in cross-linked polymer The mol% of complex structure unit (1a), constitutional repeating unit (2a).The x=2 of obtained high-molecular gel, y=2.In addition, passing through The usage amount of β CDAAmMe and Ad-AAm are adjusted, various β CDAAmMe-Ad gels (x, y) are also obtained.By that will obtain To various gels carry out at normal temperatures and pressures three days spontaneously dry, obtain xerogel.

(embodiment 11)

According to the scheme of following formulas (7-2-4), high-molecular gel is manufactured.

[chemical formula 27]

In 5mL water, by obtained in preparation example 1 as monomer (1b) β CDAAmMe24.4mg (20 μm of ol) and conduct The 4.3 μ L of isobornyl acrylate (Ib-AA) (20 μm of ol) of monomer (2b) is carried out in a manner of the concentration for respectively becoming 2mol/kG Mixing, is stirred 30 minutes at 80 DEG C when irradiating ultrasonic wave.Or it is stirred at 80 DEG C with stirring sheet.At this point, reaction Mixture becomes transparent solution.The methoxy-triethylene glycol acrylate as monomer (3b) is successively added into mixture (TEGAA) 400 μ L (1.98mmol), as polymerization initiator ammonium persulfate (relative to always rubbing for all polymerizable monomers Your number is 1mol%) and N, N, N ', N '-tetramethylethylenediamine is (relative to always rubbing for all monomersYouNumber is 1mol%), It places 30 minutes at room temperature to carry out polymerization reaction, and carries out gelation.The macromolecule comprising cross-linked polymer is obtained as a result, Gel β CDAAmMe-Ib gel (x, y).In addition, x, y respectively indicate constitutional repeating unit (1a) in cross-linked polymer, repeat The mol% of structural unit (2a).The x=2 of obtained high-molecular gel, y=2.In addition, by β CDAAmMe and Ib-AA Usage amount is adjusted, and various β CDAAmMe-Ib gels (x, y) are also obtained.By the way that obtained various gels are normal in room temperature Pressure spontaneously dry within three days, obtains xerogel.

(comparative example 5)

In addition to the scheme according to following formulas (8-2), replaced in preparation example 2 using acrylamide beta cyclodextrin (β CDAAm) Other than the obtained β CDAAmMe as monomer (1b), polymerization reaction is carried out using method same as Example 8, obtains β CDAAm-Ad gel (x, y).Acrylamide beta cyclodextrin (β CDAAm), which has from beta-cyclodextrin, to be removed one made of a hydroxyl The structure of the nitrogen atom bonding of valence group and acrylamide.

[chemical formula 28]

(comparative example 6)

Other than using 2-ethyl hexyl acrylate (Oct-AA) to replace adamantane acrylamide (Ad-AAm), utilization and comparative example 1 identical method carries out polymerization reaction, obtains α CDAAm-Oct gel (x, y).

(Blank gel, blank gel)

Acrylamide (0.29g, 4.1mmol) and methylene-bisacrylamide (13mg, 83 μm of ol) are dissolved in 0.1M In NaOH aqueous solution (2.0mL).APS (19mg, 83 μm of ol) and TEMED (12 μ L, 83 μm of ol) are added thereto, makes its gel Change.

(embodiment 12)

According to the scheme of following formulas (7-3), high-molecular gel is manufactured.

[chemical formula 29]

In 5mL water, by the γ CDAAmMe138mg (100 μm of ol) obtained in preparation example 3 as monomer (1b) and make For monomer (2b) 2-ethyl hexyl acrylate (Oct-AA) 18.4mg (100 μm of ol) in a manner of the concentration for respectively becoming 2mol/kg into Row mixing, is stirred 30 minutes at 80 DEG C when irradiating ultrasonic wave.Or it is stirred at 80 DEG C with stirring sheet.At this point, anti- Mixture is answered to become transparent solution.Into mixture successively add as monomer (3b) acrylamide (AAm) 696.6mg, Ammonium persulfate (total mole number relative to all polymerizable monomers is 1mol%) and N, N, N as polymerization initiator ', N '-tetramethylethylenediamine (relative to all monomers total mole number be 1mol%), at room temperature place 30 minutes into Row polymerization reaction, and carry out gelation.The high-molecular gel γ CDAAmMe-Oct gel comprising cross-linked polymer is obtained as a result, (x, y).In addition, x, y respectively indicate the mol% of constitutional repeating unit (1a) in cross-linked polymer, constitutional repeating unit (2a). The x=1 of obtained high-molecular gel, y=1.In addition, also having made x=0.5, y=using method identical with embodiment 12 0.5 high-molecular gel, x=0.75, high-molecular gel, the x=2 of y=0.75, high-molecular gel, the x=3 of y=2, y=3's High-molecular gel.

(embodiment 13)

In addition to the dodecylacrylate (Dod-AA) of monomer (2b) will be used as to be changed to n-butyl acrylate (Bu-AA) In addition, high-molecular gel is obtained using method same as Example 1.Obtained high-molecular gel is denoted as α CDAAmMe-Bu Gel (x, y) has obtained x=1, high-molecular gel, the x=2 of y=1, high-molecular gel, the x=3 of y=2, the macromolecule of y=3 This 3 types of gel.

(embodiment 14)

In addition to the dodecylacrylate (Dod-AA) of monomer (2b) will be used as to be changed to the just own ester of acrylic acid (He-AA) In addition, high-molecular gel is obtained using method same as Example 1.Obtained high-molecular gel is denoted as α CDAAmMe-Hex Gel (x, y) has obtained x=1, high-molecular gel, the x=2 of y=1, high-molecular gel, the x=3 of y=2, the macromolecule of y=3 This 3 types of gel.

(embodiment 15)

Other than the adamantane acrylamide for being used as monomer (2b) is changed to dihydroxypropyl adamantane esters, utilize Method same as Example 8 obtains high-molecular gel.By obtained high-molecular gel be denoted as β CDAAmMe-HAdA gel (x, Y), obtained x=1, high-molecular gel, the x=2 of y=1, high-molecular gel, the x=3 of y=2, the high-molecular gel of y=3 this 3 A type.In addition, the guest moieties of the high-molecular gel are indicated with following formula (9), the end-O- in formula (9) indicates acrylic acid The ester oxygen atom of esteratic site.

[chemical formula 30]

(embodiment 16)

Other than the adamantane acrylamide for being used as monomer (2b) is changed to acrylic acid ethyl adamantane esters, utilize Method same as Example 8 obtains high-molecular gel.By obtained high-molecular gel be denoted as β CDAAmMe-EtAdA gel (x, Y), obtained x=1, high-molecular gel, the x=2 of y=1, high-molecular gel, the x=3 of y=2, the high-molecular gel of y=3 this 3 A type.In addition, the guest moieties of the high-molecular gel are indicated with following formula (10), the end-O- in formula (9) indicates acrylic acid The ester oxygen atom of esteratic site.

[chemical formula 31]

(embodiment 17)

Other than the adamantane acrylamide for being used as monomer (2b) is changed to the dihydroxypropyl adamantane esters, Xerogel is obtained using method same as in Example 10.Obtained xerogel is denoted as β CDAAmMe-HAdA gel (x, y), Obtain x=1, high-molecular gel and xerogel, the x=2 of y=1, high-molecular gel and xerogel, the x=3 of y=2, y=3's High-molecular gel and xerogel this 3 types.

(embodiment 18)

Other than the adamantane acrylamide for being used as monomer (2b) is changed to the acrylic acid ethyl adamantane esters, Xerogel is obtained using method same as in Example 10.Obtained xerogel is denoted as β CDAAmMe-EtAdA gel (x, y), Obtain x=1, high-molecular gel and xerogel, the x=2 of y=1, high-molecular gel and xerogel, the x=3 of y=2, y=3's High-molecular gel and xerogel this 3 types.

(tension test)

" stress-strain diagram " is carried out to high-molecular gel obtained in each Examples and Comparative Examples and tests (Shimadzu " AUTOGRAPH " (model: AGX-plus) of Corporation manufacture, is observed the breaking point of high-molecular gel.This Outside, which is set as terminal, using the maximum stress until to terminal as the fracture strength of high-molecular gel.Stretching examination It tests to be fixed the lower end of high-molecular gel, implement upper end in such a way that 0.1~1mm/min of tensile speed is moved upwards.This Outside, by maximum length when stretching high-molecular gel with strain (stroke), i.e. use at this time divided by the Macromolecule before stretching Value obtained by glue length is calculated as elongation percentage.

(repeat pull)

The test film of high-molecular gel obtained in each Examples and Comparative Examples (overall length 3.5cm, No. 7 shape dumbbell shapeds) is pacified Loaded on device used in above-mentioned tension test, making high-molecular gel relative to the overall length of test film, (hereinafter referred to as " initial stage is complete It is long ") length that only extends 20%, measure proof stress at this time.Then, after the stretching for releasing test film, make macromolecule again Gel only extends 40% length relative to the initial stage overall length of test film, after measuring proof stress at this time, releases test film It stretches.Be 60,80,100,120,140,160,180,200% relative to initial stage overall length sequence repeat to implement with it is above-mentioned same The operation of sample measures respective proof stress.

(return rate)

After xerogel is cut off, section is adhered by each other, using with it is disconnected after same method measurement T (day) Split stress.Then, the value for calculating " (disruptive force before fracture strength/cutting after T (day)) × 100 ", as return rate.

Stress-strain diagram (the fracture strength song of the α CDAAmMe-Dod gel (x, y) of Examples 1 to 6 is shown in Fig. 2 Line).(1) of Fig. 2~(6) are respectively (x, y)=(1,1), (2,2), (3,3), (4,4), (5,5), (6,6).

The fracture strength curve of the α CDAAm-Dod gel (3,3) of the not linking group of comparative example 1 is shown in Fig. 3.This Outside, the result of the fracture strength curve of the α CDAAm-Dod gel of (x, y)=(4,4), (5,5) (6,6) is also shown together.

It is confirmed according to Fig. 3 with the comparison of the result of Fig. 2: compared with α CDAAm-Dod gel, even if being same content, α The stress of CDAAmMe-Dod gel, strain are also improved.Therefore, it can be said that α CDAAmMe-Dod gel has frequently The toughness high compared with the α CDAAm-Dod gel of example 1.

Fig. 4 shows previously known 6 kinds of acrylamide gels, and (the respective methylene-bisacrylamide in (1)~(6) is crosslinked Measure the result of the fracture strength curve for 1~6mol%).The insertion figure of the chart of Fig. 4 is the region that strain is 0~100% Expanded view.Know stress, strain differential compared with the α CDAAmMe-Dod gel of embodiment.According to the result, it may be said that α CDAAmMe-Dod gel has high tenacity.

Shown in Fig. 5 the α CDAAmMe-Oct gel (x, y) of embodiment 7 fracture strength curve ((x, y)=(3,3), (2,2) (1,1), (0.75,0.75).

It is shown in Fig. 6 based on the measurement for carrying out 3 Fig. 5 as a result, summarizing the result of the fracture strength of each sample.

Be shown without in Fig. 7 the α CDAAm-Oct gel (x, y) of linking group fracture strength curve ((x, y)=(3, 3), (2,2) (1,1), (0.75,0.75), (0.5,0.5).

It is shown in Fig. 8 based on the measurement for carrying out 3 Fig. 7 as a result, summarizing the result of the fracture strength of each sample.

According to Fig. 5,6 and Fig. 7,8 comparison it is found that with linking group α CDAAmMe-Oct gel (x, y) have than The toughness for not having the α CDAAm-Oct gel of linking group high.

α CDAAmMe-Dod gel (x, y), α CDAAm-Dod gel (x, y) and the AAm as Blank gel are shown in Fig. 9 The summary of the stress result of gel (methylene-bisacrylamide crosslinked acrylamide gel).

In addition, it is (sub- to show α CDAAmMe-Dod gel (x, y), α CDAAm-Dod gel (x, y) and AAm gel in Figure 10 Bisacrylamide crosslinked acrylamide gel) strain result summary.

According to Fig. 9,10 result it is found that the stress characteristics of α CDAAmMe-Dod gel, emergent property than α CDAAm- Dod gel is excellent.Although emergent property ratio α CDAAmMe-Dod gel is poor in addition, knowing that AAm gel has high stress.

The repeat pull of α CDAAmMe-Dod gel (3,3) and α CDAAm-Dod gel (3,3) is shown in Figure 11 As a result.

According to the result of Figure 11 it is found that α CDAAmMe-Dod gel (3,3) is with higher than α CDAAm-Dod gel (3,3) Stress, it may be said that there is high tenacity.In addition, display α CDAAmMe-Dod gel (3,3) maintains fracture strength and does not remain by prolonging Stretch caused trace.Therefore, show that α CDAAmMe-Dod gel (x, y) has self-repairability.

Shown in Figure 12 β CDAAmMe-Ad gel (x, y) fracture strength curve ((x, y)=(6,6), (5,5), (4, 4), (3,3), (2,2), (1,1), (0.75,0.75), (0.5,0.5)).

Be shown without in Figure 13 the β CDAAm-Ad gel (x, y) of linking group fracture strength curve ((x, y)=(5, 5), (4,4), (3,3), (2,2), (1,1)).

According to Figure 12,13 result is it is found that β CDAAmMe-Ad gel has the stress more excellent than β CDAAm-Ad gel special Property.

The fracture strength curve ((x, y) of the xerogel of the β CDAAmMe-Ad gel (x, y) of embodiment 10 is shown in Figure 14 =(3,3), (2,2), (1,1), (0.75,0.75), (0.5,0.5)).According to the result of Figure 14 it is found that xerogel also have it is excellent Different stress characteristics.

The fracture strength curve ((x, y) of the xerogel of the β CDAAmMe-Ib gel (x, y) of embodiment 11 is shown in Figure 15 =(3,3), (2,2), (1,1), (0.75,0.75), (0.5,0.5)).According to the result of Figure 15 it is found that xerogel also have it is excellent Different stress characteristics.

The result of the fracture strength curve of the xerogel of acrylamide gel (TEGAA crosslinking) is shown in Figure 16.Known to The β CDAAmMe-Ib gel (x, y) of embodiment 11 is compared, stress, strain differential.According to the result alternatively β CDAAmMe-Ib Gel has high tenacity.

Shown in Figure 17 γ CDAAmMe-Oct gel (x, y) fracture strength curve ((x, y)=(3,3), (2,2), (1, 1), (0.75,0.75), (0.5,0.5)).According to the result it is found that γ CDAAmMe-Oct gel (x, y) is also because of linker regiment headquarters Presence, strain rate is largely increased, it is known that especially at (x, y)=(1,1) with excellent stress characteristics.

The sample of the physical property of the high-molecular gel α CDAAmMe-Oct gel (1,1) of display evaluation embodiment 7 is shown in Figure 18 The photo of son.

In the puncture test of Figure 18 (a), fracture etc. is not observed in α CDAAmMe-Oct gel (1,1).Therefore, may be used Know that the high-molecular gel has high tenacity.

Figure 18 (b), (c) tension test in, also do not observed in α CDAAmMe-Oct gel (1,1) fracture etc., And it knows to be restored after experiment to original shape.

Figure 18 (d) selfreparing test in, it is known that by make fracture α CDAAmMe-Oct gel (1,1) be adhered by and It repairs for original gel.Therefore, which has self-repairability.

Figure 19 show α CDAAmMe-Bu gel (x, y), α CDAAmMe-Hex gel (x, y) measurement result (each sample Column diagram successively indicates (x, y)=(1,1), (2,2), (3,3) since left).It knows to be provided with high tenacity.

It is solidifying that Figure 20 shows β CDAAmMe-Ib gel (x, y) (in Figure 20, being labeled as β CDAAmMe-Ibr), β CDAAmMe-Ad Glue (x, y) (in Figure 20, being labeled as β CDAAmMe-AdAAm), β CDAAmMe-HAdA gel (x, y), β CDAAmMe-EtAdA are solidifying The measurement result of glue (x, y) (column diagram of each sample successively indicates (x, y)=(1,1), (2,2), (3,3) since left).It can Know and is provided with high tenacity.

Figure 21 shows return rate measurement result of the various xerogel of embodiment 10,11,17,18 at T=2 and 5 day.Known to Arbitrary xerogel shows excellent return rate.

Figure 22 indicates the temperature of return rate of the xerogel ((x, y)=(2,2)) after T=2 days obtained in embodiment 10 Dependence.Specifically, Figure 22 is indicated after being adhered by the xerogel after cutting immediately in defined temperature (25,50,75,100 DEG C) kept for 2 days under environment, then, carry out the variation of the return rate when measurement of the return rate.It can be seen from this result that restoring Rate depends on temperature.

Figure 23 is indicated after cutting off xerogel obtained in embodiment 10 ((x, y)=(2,2)), in the environment of 100 DEG C Make the relationship of the recovery time and return rate when its recovery.It knows before by the regular hour, return rate slowly improves.

It may be said that above result is supported by the friendship of the constitutional repeating unit comprising general formula (1a) and general formula (2a) expression The high-molecular gel that linked polymer is constituted has high tenacity and has self-repairability.

Industrial applicibility

High molecular material of the invention is the material for having high tenacity and self-repairability.Therefore, as have both can resistance to practicality The obdurability of rank, ductility, self-repairability and durability material, it can be expected that impact absorbing material or tire layer, from Repair the application in the various uses such as film, self-repairability adhesive.

Claims

1. a kind of high molecular material, to include crosslinking made of being crosslinked by the interaction of main group and guest moieties The high molecular material of polymer, wherein

The cross-linked polymer includes the constitutional repeating unit that following general formulas (1a) and general formula (2a) indicate,

[chemical formula 1]

In formula (1a), Ra indicates hydrogen atom or methyl, R^HIndicate main group, R¹It indicates hydroxyl, sulfydryl, can have 1 or more The alkoxy of substituent group, can have 1 or more substituent group thio alkoxy, can have 1 or more substituent group alkyl, The amino that can have 1 substituent group, the amide groups that can have 1 substituent group, by from selected from the group that is made of aldehyde radical and carboxyl In univalent perssad in remove 1 hydrogen atom and the bivalent group that is formed,

[chemical formula 2]

In formula (2a), Ra indicates hydrogen atom or methyl, R^GIndicate guest moieties, R²It indicates hydroxyl, sulfydryl, can have 1 or more The alkoxy of substituent group, can have 1 or more substituent group thio alkoxy, can have 1 or more substituent group alkyl, The amino that can have 1 substituent group, the amide groups that can have 1 substituent group, by from selected from the group that is made of aldehyde radical and carboxyl In univalent perssad in remove 1 hydrogen atom and the bivalent group that is formed.

2. high molecular material according to claim 1, wherein the main group is selected from by alpha-cyclodextrin, β-ring paste At least one of the group of essence and gamma-cyclodextrin composition.

3. high molecular material according to claim 1 or 2, wherein the main group is alpha-cyclodextrin, the object base Group is at least one of the group selected from octyl and dodecyl.

4. high molecular material according to claim 1 or 2, wherein the main group is beta-cyclodextrin, the object base Group is at least one of the group selected from adamantyl and isobornyl.

5. high molecular material according to claim 1 or 2, wherein the main group is gamma-cyclodextrin, the object Group is at least one of the group selected from octyl and dodecyl.

6. a kind of manufacturing method of high molecular material, for comprising being crosslinked by the interaction of main group and guest moieties Made of cross-linked polymer high molecular material manufacturing method,

The polymerization reaction of its mixture for having the polymerizable monomer by the inclusion of following general formulas (1b) and general formula (2b) expression And the process for obtaining the cross-linked polymer,

[chemical formula 3]

In formula (1b), Ra indicates hydrogen atom or methyl, R¹And R^HRespectively with the R of above-mentioned general formula (1a)¹And R^HIt is identical,

[chemical formula 4]

7. the manufacturing method of high molecular material according to claim 6, wherein the mixture includes to pass through the general formula The interaction of the guest moieties of the main group of (1b) and the general formula (2b) and by the general formula (1b) and general formula (2b) table The inclusion compound that the polymerizable monomer shown is formed.

8. a kind of polymerizable monomer composition, for for manufacturing the combination of polymerizable monomer used in the raw material of high molecular material Object, it includes following general formulas (1b) indicate polymerizable monomer and following general formula (2b) indicate polymerizable monomer,

[chemical formula 5]

[chemical formula 6]

9. polymerizable monomer composition according to claim 8, it includes the polymerisms indicated by the following general formula (1b) The interaction of the guest moieties of polymerizable monomer that the main group of monomer and the following general formula (2b) are indicated and by the general formula The inclusion compound that the polymerizable monomer that the polymerizable monomer and the general formula (2b) that (1b) is indicated indicate is formed,

[chemical formula 7]

[chemical formula 8]

10. a kind of polymerizable monomer, to include to be crosslinked by the interaction of main group and guest moieties for manufacturing Made of cross-linked polymer high-molecular gel polymerizable monomer, indicated by following general formula (1b),

[chemical formula 9]

In formula (1b), Ra indicates hydrogen atom or methyl, R^HIndicate main group, R¹It indicates hydroxyl, sulfydryl, can have 1 or more The alkoxy of substituent group, can have 1 or more substituent group thio alkoxy, can have 1 or more substituent group alkyl, The amino that can have 1 substituent group, the amide groups that can have 1 substituent group, by from selected from the group that is made of aldehyde radical and carboxyl In univalent perssad in remove 1 hydrogen atom and the bivalent group that is formed.

11. a kind of preparation method of the polymerizable monomer replaced through host molecule comprising in the presence of acid catalyst, under making The process that the polymerizable monomer and host molecule for stating general formula (5) expression carry out dehydrating condensation in a solvent,

[chemical formula 10]

In formula (5), Ra indicates hydrogen atom or methyl, R¹Indicate hydroxyl, sulfydryl, can have 1 or more substituent group alkoxy, Can have the thio alkoxy of 1 or more substituent group, the substituent group that can have 1 or more alkyl, can have 1 substituent group Amino, can have 1 substituent group amide groups, by the univalent perssad from selected from the group being made of aldehyde radical and carboxyl The bivalent group formed except 1 hydrogen atom.